Coated glasses having a low sheet resistance, a smooth surface, and/or a low thermal emissivity

ABSTRACT

A glass sheet has an electrically conductive film having a sheet resistance in the range of 9.5 to 14.0 ohms/square; an emissivity in the range of 0.14 to 0.17 and an absorption coefficient of greater than 1.5×103 cm−1 in the wavelength range of 400-1100 nanometers, and a surface roughness of less than 15 nanometers Root Means Square. A glass sheet of another embodiment of the invention has an electrically conductive film having a phosphorous-fluorine doped tin oxide pyrolytically deposited film on the surface of the glass sheet, wherein the ratio of phosphorous precursor to tin precursor is in the range of greater than 0-0.4. The coated glass sheets of the invention can be used in the manufacture of multi sheet insulating units, OLEDs and solar cells.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. application Ser. No.13/736,316, filed Jan. 8, 2013 and titled COATED GLASSES HAVING A LOWSHEET RESISTANCE, A SMOOTH SURFACE, AND/OR A LOW THERMAL EMISSIVITY,which claimed priority to U.S. Provisional Patent Application Ser. No.61/584,837 filed Jan. 10, 2012 and titled COATED GLASSES HAVING A LOWSHEET RESISTIVITY, A SMOOTH SURFACE, AND/OR A LOW THERMAL EMISSIVITY,all of which applications are herein incorporated by reference in theirentirety.

BACKGROUND OF THE INVENTION 1. Field of the Invention

This invention relates to coated glasses having a low sheet resistance,a smooth surface and/or a low thermal emissivity, and more particularly,to a pyrolytic fluorine doped tin oxide coating having a low sheetresistance, e.g. below 14 ohms/square, a smooth outer coating surface,e.g. an outer coating surface roughness of less than 15 nanometers(“nm”) root mean square, and/or a low thermal emissivity.

2. Discussion of the Technology

As is appreciated by those skilled in the coating art, glass sheets arecoated to, among other things, provide a coated glass having optical,physical and electrical properties different from the optical, physicaland electrical properties of the uncoated glass. By way of illustrationand not limiting to the discussion, a pyrolytic chemical vapordeposition (“CVD”) coating of fluorine doped tin oxide deposited onglass provides a coated glass having visible and infrared transmission,percent haze, emissivity, surface roughness, and sheet resistance, e.g.sheet resistance different from the sheet resistance of the uncoatedglass sheet.

Unfortunately, altering one set of properties can result in another setof properties to be outside a desired range. For example, and notlimiting to the discussion, decreasing the sheet resistance of afluorine doped tin oxide coating by increasing the coating thickness,e.g. as disclosed in column 3, lines 59-68 of U.S. Pat. No. 3,677,814(“USPN '814”) increases the surface roughness. The limitation associatedwith increasing the surface roughness by increasing the coatingthickness can be reduced by increasing the fluoride content of theorganic tin composition, e.g. as disclosed in column 4, lines 30-34 ofU.S. Pat. No. 3,107,177 (“USPN '177”). The drawback with this techniqueis that large additions of fluorine, above a certain level, e.g.ammonium fluoride, are not effective, e.g. as disclosed in column 3,lines 41-53 of USPN '814 in increasing the conductivity of the coatingwhich reduces the sheet resistance.

As can now be appreciated, it would be advantageous to provide atechnique to alter the properties of CVD fluorine doped tin oxidecoating to, among other things, decrease sheet resistance with nominalincrease in coating thickness; reduce the surface roughness of thecoating and/or decrease the thermal emissivity of the coating.

SUMMARY OF THE INVENTION

This invention relates to a coated glass sheet including, among otherthings, a glass substrate, and an electrically conductive film over asurface of the glass substrate, the conductive film including, amongother things, a sheet resistance in the range of 9.5 to 14.0ohms/square; an emissivity in the range of 0.14 to 0.17 and anabsorption coefficient of greater than 1.5×10³ cm⁻¹ in the wavelengthrange of 400-1100 nanometers, and a Surface height mean square of lessthan 15 nanometers, wherein the properties are determined at a substratethickness of 3.2 millimeters.

The invention further relates to a coated glass sheet including, amongother things, a glass substrate, and an electrically conductive filmover a surface of the glass substrate, the electrically conductive filmincluding, among other things comprising a doped tin oxide pyrolyticallydeposited film on a surface of the glass substrate, wherein dopant ofthe doped tin oxide film is fluorine and a co-dopant or alloyingconstituent selected from the group of phosphorous, boron and mixturesof phosphorous and boron.

The invention still further an article of manufacture including, amongother things, a glass substrate, and an electrically conductive filmover a surface of the glass substrate, the conductive film selected froma group comprising Embodiment A, Embodiment B and Embodiment c, whereinthe conductive film of Embodiment A includes, among other things, asheet resistance in the range of 9.5 to 14.0 ohms/square; an emissivityin the range of 0.14 to 0.17 and an absorption coefficient of greaterthan 1.5×10³ cm⁻¹ in the wavelength range of 400-1100 nanometers, and aSurface height root mean square of less than 15 nanometers, wherein theproperties are determined at a substrate thickness of 3.2 millimeters;the conductive film of Embodiment B includes, among other things, aphosphorous-fluorine doped tin oxide pyrolytically deposited film overthe surface of the glass sheet, wherein coating vapor of the depositedfilm comprises a tin precursor, a phosphorous precursor and a fluorineprecursor, and the ratio of the phosphorous precursor to the tinprecursor is in the range of greater than 0 to 0.4, and the conductivefilm of Embodiment C includes, among other things a boron-fluorine dopedtin oxide pyrolytically deposited film over the surface of the glasssheet, wherein coating vapor of the deposited film comprises a tinprecursor, a boron precursor and a fluorine precursor, and the ratio ofthe boron precursor to the tin precursor is in the range 0 to 0.4.

DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross-sectional view of the exit end of a float glassforming chamber that can be used in the practice of the invention.

FIGS. 2-4 are side views of non-limiting embodiments of pieces of coatedglass ribbons incorporating features of the invention.

FIG. 5 is a copy of a photograph of crystal orientation of a fluorinedoped tin oxide film of the prior art.

FIG. 6 is a copy of a photograph of crystal orientation of a fluorinedoped tin oxide film of the invention.

FIG. 7 is an isometric view of a coated glass sheet of the invention.

FIG. 8 is a sectional view of an edge assembly of a multi-sheetinsulating unit incorporating features of the invention.

FIG. 9 is a cross sectional view of a multi-sheet unit incorporatingfeatures of the invention.

FIG. 10 is an elevated side view of an organic light emitting diodeincorporating features of the invention.

FIG. 11 is an elevated side view of a solar cell incorporating featuresof the invention.

DETAILED DESCRIPTION OF THE INVENTION

As used herein, spatial or directional terms such as “inner”, “outer,and the like, relate to the invention as it is shown in the drawing ofthe figures. However, it is to be understood that the invention canassume various alternative orientations and, accordingly, such terms arenot to be considered as limiting. Further, all numbers expressingdimensions, physical characteristics, and so forth, used in thespecification and claims are to be understood as being modified in allinstances by the term “about”. Accordingly, unless indicated to thecontrary, the numerical values set forth in the following specificationand claims can vary depending upon the property desired and/or sought tobe obtained by the present invention. At the very least, and not as anattempt to limit the application of the doctrine of equivalents to thescope of the claims, each numerical parameter should at least beconstrued in light of the number of reported significant digits and byapplying ordinary rounding techniques. Moreover, all ranges disclosedherein are to be understood to encompass any and all sub ranges subsumedtherein. For example, a stated range of “1 to 10” should be consideredto include any and all sub ranges between and inclusive of the minimumvalue of 1 and the maximum value of 10; that is, all sub rangesbeginning with a minimum value of 1 or more and ending with a maximumvalue of 10 or less, e.g., 1 to 6.7, or 3.2 to 8.1, or 5.5 to 10. Also,as used herein, the term “mounted over” or “coated over” means over butnot necessarily in surface contact with. For example, one article orcomponent of an article “mounted over” or “coated over” another articleor component of an article does not preclude the presence of materialsbetween the articles, or between components of the article,respectively.

Before discussing several non-limiting embodiments of the invention, itis understood that the invention is not limited in its application tothe details of the particular non-limiting embodiments shown anddiscussed herein since the invention is capable of other embodiments.Further, the terminology used herein to discuss the invention is for thepurpose of description and is not of limitation. Still further, unlessindicated otherwise, in the following discussion like numbers refer tolike elements.

In general, but not limiting to the invention, the preferrednon-limiting embodiments of the invention are directed to a doped tinoxide layer applied by a chemical vapor deposition (known in the art as“CVD”) pyrolytic coating method on a soda-lime silica glass substrate toprovide the glass substrate with initial properties that in subsequentembodiments of the invention are enhanced. For a full appreciation ofthe invention, specific non-limiting embodiments of the invention willbe discussed separately. The specific embodiments of the inventionrelate to, but are not limited to, Section (1) directed to a crystallinedoped tin oxide coating over or on a surface of a glass substrate;Section (2) directed to an amorphous doped tin oxide film coated on orover a surface of a glass substrate, and Section (3) directed to the useof the coated substrates of Sections (1) and (2).

Non-limiting embodiments of the invention will be directed to coatingsapplied to a soda-lime-silicate continuous glass ribbon made by thefloat process. The invention, however, is not limited thereto and thecoating can be applied to any type of substrate, e.g. metal, plastic,glass of any composition that is structurally stable at or above thecoating temperature, for example but not limited to 400 degreesFahrenheit (“° F.”). Further, the coating can be applied to glass havingany shape, for example, but not limited to flat glass sheets, shapedglass sheets, e.g. but not limited to shapes for automotive windows,aircraft windows, home and commercial windows and windows for cabinets,e.g. refrigerators and ovens.

Section (1): Non-Limiting Embodiments of the Invention Directed to aCrystalline Doped Tin Oxide Coating Over or on a Surface of a GlassSubstrate

In a preferred non-limiting embodiment of the invention, the doped tinoxide layer is a fluorine doped tin oxide layer applied over or on acolor suppression layer by the CVD pyrolytic coating process(hereinafter also referred to as the “CVD process”). In the preferredpractice of the invention, the doped tin oxide layer of the inventionand the color suppression layer are applied to a surface of a continuousglass ribbon. More particularly, and with reference to FIG. 1, acontinuous glass ribbon 22 floating on a pool of molten metal 24 movesin the direction of arrow 23. The pool of molten metal 24 is containedin a glass forming chamber 26, e.g. but not limited to the typedisclosed in U.S. Pat. Nos. 3,333,936 and 4,402,722, which patents arehereby incorporated by reference. As the glass ribbon 22 moves under afirst CVD coater 28, a color suppression film, an anti-Iridescence film,or an underlayer film 30 is applied to surface 32 of the glass ribbon 22(see also FIG. 2). The surface 32 of the ribbon 22 is opposite tosurface 33 of the ribbon 22 supported on the pool 24 of molten metal.Continued movement of the glass ribbon 22 in the direction of arrow 23moves the glass ribbon 22 under a second CVD coater 34 to apply a dopedtin oxide film 36 (see FIG. 2) of the invention onto surface 38 of thecolor suppression film 30. As used herein, the term “color suppression”unless indicated otherwise includes “anti-iridescence”.

In the preferred practice of the invention, the color suppression film30 is a gradient layer of tin oxide and silicon oxide, and is of thetype disclosed in U.S. Pat. Nos. 5,356,718 and 5,863,337, which patentsare hereby incorporated by reference. The percent of silicon oxide inthe color suppression film 30 decreases as the distance from the surface32 of the glass ribbon 22 increases to provide a gradient colorsuppression film 30 having 95-100% silicon oxide at the surface 32 ofthe glass ribbon and 95-100% tin oxide at the surface 38 of the colorsuppression film 30 (see FIG. 2). For a detailed discussion of thechemistry and application of the color suppression film 30 reference canbe made to U.S. Pat. Nos. 5,356,718 and 5,863,337.

As can now be appreciated by those skilled in the art, the invention isnot limited to a gradient color suppression film, and the inventioncontemplates a color suppression layer having a plurality of homogeneoussilicon oxide and tin oxide films. More particularly and not limiting tothe invention, shown in FIG. 3 is a color suppression layer 42 havingtin oxide films 44 and 46 alternating with silicon oxide films 50 and51. Optionally the color suppression film 30 and the color suppressionlayer 42 can be omitted, and the doped tin oxide film 36 of theinvention can be applied directly to the surface 32 of the glass ribbon22 as shown in FIG. 4.

For a full appreciation of this non-limiting embodiment of theinvention, the doped tin oxide layer of the invention will be discussedapplied to the mixed metal oxides film 30, however, the invention is notlimited thereto and can be applied to the color suppression layer 42(FIG. 3), or applied directly to the surface 32 of the glass ribbon (seeFIG. 4). In the preferred practice of the invention, the doped tin oxideis fluorine-doped tin oxide, the invention, however, is not limitedthereto and can be practice with other doped tin oxides, e.g. but notlimited to tin oxides doped with antimony and mixtures of fluorine andantimony. At the present time there is available a coated glass productsold by PPG Industries, Inc. under the trademark Sungate® 500. TheSungate® 500 coated glass has the mixed metal oxides color suppressionfilm 30 and a fluorine doped tin oxide layer 52. For purposes of claritythe coated glasses of this non-limiting embodiment of the invention willbe referred to as “Enhanced Coated Glass” or “ECG” and the Sungate® 500coated glass will be referred to as “Standard Coated Glass”. Theproperties of the Standard Coated Glass and the ECG of interest in thepresent discussion, but not limiting to the invention, are presented inTable 1 below.

TABLE 1 STANDARD ENHANCED COATED PROPERTY COATED GLASS GLASS Glassthickness 3.2 millimeters 3.2 millimeters Sheet resistance 20.0-22.0ohms/sq^(a) 9.5-14.0 ohms/sq Emissivity 0.20-0.22 0.14-0.17 ThicknessUnderlayer 30 80-100 nm^(b) 80-100 nm F:SnO2 layer 310-350 nm 420-540 nmReflected Color^(c) a* −6.0, +4.0 −6.0, +4.0 b* 0.0, −10.0 +3.0, −7.0 L*37.0-41.0 37.0-41.0 Haze^(d) Less than 1% Less than 1% Transmittance^(e)Greater than 82.0% Greater than 80.0% Surface roughness Greater than 20nm RMS Less than 15 nm RMS^(f) Absorption Greater than 1.9 × 10³ cm⁻¹Greater than Coefficient^(g) 1.5 × 10³ cm⁻¹ Coefficient of Less than 1.2Less than 1.2 friction Notes: ^(a)Abbreviation for “ohms/square”.^(b)Abbreviation for “nanometers”. ^(c)Reflected Color is given in theL*, a*, b* coordinates, using CIE Illuminant D65, 10 degree Observer.^(d)The Standard Coated Glass usually has a measured haze in the rangeof 0.1-0.3%, and the ECG is expected to have a measured haze in therange of 0.4-0.6%. ^(e)Transmittance is visible transmittance in thewavelength range of 380-780 nanometers (“nm”), using CIE Illuminant C, 2degree Observer. ^(f)RMS is an abbreviation for root means square. TheRMS of the coated surface was measured using Atomic Force Microscopy.^(g)The absorption coefficient of the conductive coating layer ismeasured in a wavelength region between 400 and 1100 nm.

The thickness of the mixed metal oxide film 30 and the fluorine dopedtin oxide films 36 and 52 were measured using a profliometer. The sheetresistivity was measured using a four point probe. The emissivity wasdetermined from measurement of reflectance in the infrared wavelengths.The surface RMS was measured using atomic force microscopy. Thereflected color is determined as described in ASTM E 308-90 and otherinternational standards from measurement of reflectance in the range of380 to 780 nm of the electromagnetic scale. The visible transmittance isin the range of 380 to 780 nm of the electromagnetic scale. The visibletransmittance is measured using C.I.E. standard illuminant “C” with a 2′observer over a wavelength range of 380 to 780 nanometers.

The absorption coefficient was measured in the following manner.Methylene iodide with a refractive index of 1.79 was applied to aconductive film deposited on a glass sheet, and a cover piece of clearfused quartz with a thickness of 1 mm was allowed to adhere to themethylene iodide, thus producing a comparative sample in which ascattering loss due to surface roughness of the conductive film was nolonger caused. The transmittance and reflectance of the comparativesample in the visible and near-infrared light region were measured usinga spectrophotometer, and from these results the absorbance wasdetermined. A reference sample was made by applying methylene iodide toa glass sheet with no conductive film being formed thereon and the coverglass was allowed to adhere, thus obtaining a reference sample. Theglass sheet for the comparative sample and reference sample had the samecomposition. Similarly in this reference sample, the absorbance in thevisible and near-infrared light region was determined as in the above.The absorption coefficient of the conductive film was determined bysubtracting the absorbance of the reference sample from that of thecomparative sample and solving an equation in which multiple reflectionsis taken into consideration. When the conductive film of the comparativesample was formed on an undercoating film, one in which an undercoatingfilm was formed under the same conditions was used as a referencesample.

The coefficient of friction is measured according to the ASTM D-1894test where a specimen is traversed under a 200 gram sled. Thecoefficient of friction is defined as the ratio Ft/Fn, where Ft is thenormal force or the force which presses the two surfaces together(weight of the sled) and Fn is the tractive force required to initiate(static) and maintain (kinetic) relative motion between the surfaces.The test measures the resistance between the coating and the sledsurface, where a high resistance indicates rougher surface and a lowresistance indicates a smoother surface. In the practice of theinvention, the coefficient of friction is preferably less than 1.2, morepreferably less than 1.0 and most preferably less than 0.8

The underlayer 30 of the ECG is similar to the underlayer 30 of thestandard coated glass and each include the mixed metal oxides film 30 ofSiO₂ and SnO₂ between a clear glass ribbon or substrate 22 and afluorine doped tin oxide film; the fluorine doped tin oxide film for theECG is designated by number 36, and the fluorine doped tin oxide filmfor the standard coated glass is designated by number 52 (see FIGS.2-4). As discussed above, the mixed metal oxides film 30 and thefluorine doped tin oxide films 36 and 52 are applied by the CVDpyrolytic coating process.

The chemistry for the fluorine doped tin oxide film 36 for the ECG, andthe fluorine doped tin oxide film 52 of the standard coated glass ispresented in following Table 2.

TABLE 2 STANDARD COATED ENHANCED COATED GLASS GLASS CHEMISTRY ChemistryFlows MBTC^(h) 28-30 (Lb/cell/hr)^(i) 42-46 (Lb/cell/hr) TFA^(j) 4.5-6.0(Lb/cell/hr) 8.5-10.5 (Lb/cell/hr) Water 5-7 (Lb/cell/hr) 11-13(Lb/cell/hr) CA^(k) 50 SCFM/cell^(l) 40 SCFM/cell F/Sn^(m) 0.005-0.007Greater than 0.007-0.010 F wt %^(n) 0.085-0.89  0.090-0.110 Notes:^(h)“MBTC” is the chemical abbreviation for monobutylin trichloride,which is the tin precursor. ^(i)“Lb/cell/hr” is the abbreviation for“pounds per coating cell per hour”. ^(j)“TFA” is the chemicalabbreviation for trifluoroacetic acid, which is the fluorine precursor.^(k)“CA” is the abbreviation for carrier air. In the practice of theinvention, the carrier gas is air which is about 21% oxygen. Theinvention contemplates using other concentrations of oxygen up to andincluding 100%. ^(l)“SCFM” is abbreviation for “standard cubic feet perminute”. ^(m)“F/Sn” is the atomic ratio of fluorine to tin in thefluorine doped tin oxide coating. ^(n)“Fwt %” is the weight percent offluorine in the fluorine doped tin oxide coating.

One non-limiting embodiment of the ECG of the invention is an emissivityin the range of 0.14-0.17 and a sheet resistivity of 9.5 to 14.0ohms/square. As is known in the art, the emissivity of a material is therelative ability of its surface to emit energy by radiation. It is theratio of energy radiated by a particular material to energy radiated bya black body at the same temperature. A true black body would have anε=1 while any real object would have ε<1. Emissivity is a dimensionlessquantity. The Standard Coated Glass has an emissivity in the range of0.20-0.22, and the ECG has an emissivity in the range of 0.14-0.17.

The lower emissivity range of the ECG can be obtained by increasing theamount of fluorine in, or by increasing the thickness of, the fluorinedoped tin oxide layer. Increasing fluorine in the fluorine doped tinoxide layer increases the number of free electrons in the fluorine dopedtin oxide layer and thus the conductivity and reflectivity of thefluorine doped tin oxide layer increases and the emissivity of thefluorine doped tin oxide layer decreases. From the above discussion, itcan be appreciated that the emissivity, and sheet resistance, of thedoped tin oxide layer are related to one another, and a measure of thesheet resistance can be used to approximate the emissivity of the dopedtin oxide layer.

Using the fluorine doped tin oxide film 52 of the Standard Coated Glassas the starting point, the emissivity of the ECG can be obtained byincreasing the thickness of the fluorine doped tin oxide film 52 of theStandard Coated Glass to increase the fluorine in the fluorine doped tinoxide film 36 of the ECG, and/or by increasing the fluorine to tin ratio(“F/Sn”) in the fluorine doped tin oxide film 52 of the Standard CoatedGlass to increase the fluorine in the fluorine doped tin oxide film 36of the ECG.

The inventors recognized that the doped tin oxide layer is a crystallinelayer and that increasing the thickness of the doped tin oxide layerincreases the crystal size and increases haze. More particularly,increased crystal growth provides a rough surface that puts a drag onthe material used to clean the surface of the doped tin oxide film 52.It has been observed that when the material is paper, e.g. paper towels,the rough surface of the tin oxide film 52 (see FIG. 2) can tear thepaper towel as it is pulled across the surface of the fluorine doped tinoxide film 46.

The inventors further recognized that lowering the emissivity byincreasing the F/Sn ratio has a limited ratio, e.g. read column 4, lines30-34 of USPN '177. In view of the forgoing, the emissivity of the ECGis attained by increasing the F/Sn atomic ratio to a value within therange of 0.006-0.010 and increasing the thickness of the fluorine dopedtin oxide layer to thickness within the range of 500-540 nm. It wasexpected that increasing the thickness range of 310-350 nm of thefluorine doped tin oxide film 46 to the thickness range of 500-540 nm ofthe fluorine doped tin oxide film 36 of the ECG would increase thesurface roughness of the ECG. However, the unexpected occurred. Moreparticularly, the Standard Coated Glass having a thinner fluorine dopedtin oxide film 52 than the fluorine doped tin oxide film 36 of the ECGhad a surface roughness greater than 20 nm RMS, and the ECG had asurface roughness of less than 15 nm RMS.

Although it is not clearly understood, it is believed that the ECG has athicker fluorine doped tin oxide film 36 and a lower surface roughnessvalue than the Standard Coated Glass as a result of the interaction ofthe chemicals during deposition.

More particularly, the flow per cell of the TFA is increased for the EFGto increase the incorporation of fluorine in the fluorine doped tinoxide film 36, and the flow per cell of the MBTC and the flow per cellof water is increased to increase the coating deposition rate of theMBTC and the thickness of the fluorine doped tin oxide film 36 of theECG. Increasing the fluorine of the fluorine doped tin oxide film 36 forthe ECG increases the F/Sn ratio to attain the desired emissivity andsheet resistance as discussed above. More particularly, the system forcoating the Standard Coated Glass and for coating the Enhanced CoatedGlass uses compressed air to move the vapors of the MBTC, TFA and waterinto the cell and uses nitrogen to move the mixed vapors of MBTC, TFAand water out of the cell toward the surface 32 of the glass ribbon 22to deposit the fluorine doped tin oxide film 36 and 52 over theunsupported surface 32 of the glass ribbon 20. The total volumetric flowrate of coating vapors (vapors of MBTC, TFA and water), compressed airand nitrogen are maintained within a range of 50-75 SCFM. Increasing thevapor flow of the coating vapors requires decreasing the flow rate ofthe carrier air and/or nitrogen to remain within the total volumetricflow rate of 50-75 SCFM

FIG. 5 is a copy of a photograph of the crystal structure of theStandard Coated Glass, and FIG. 6 is a copy of a photograph of thecrystal structure of the ECG. The crystal structure of the ECG is moreuniform in size and more compact than the crystal structure for theStandard Coated Glass. The proportion of crystallographic orientation ofthe crystals for the Standard Coated Glass is (200) followed by (110),and the orientation of the crystals for the ECG is (200) followed by(211). The crystal orientation was measured by Θ/2Θ (theta/2theta) x-raydiffraction.

Coating the glass with the ECG chemistry, the surface height of the ECGwas reduced to provide the ECG with a smoother coated surface than thecoated surface of the Standard Coated Glass.

The above numbers are for a glass ribbon having a thickness of 3.2millimeters (see Table 1). As is appreciated by those skilled in theart, increasing the thickness of the glass ribbon, while maintaining thevolume of glass produced, decreases the ribbon speed, and preferably theflow of the coating vapors is decreased to maintain the thickness of thecolor suppression film 30 and layer 42, and the thickness of thefluorine doped tin oxide films 36, 52. Further, decreasing the thicknessof the glass ribbon increases the ribbon speed, and preferably the flowof the coating vapors is increased to maintain the thickness of thecolor suppression film 30 and layer 42, and the thickness of thefluorine doped tin oxide films 36, 52.

Section (2): Non-Limiting Embodiments of the Invention Directed to anAmorphous Doped Tin Oxide Film Coated on or Over a Surface of a GlassSubstrate

As discussed above in Section (1) the crystal structure of the ECG wasaltered by, among other things, making changes in the weight percent ofthe components of the coating chemistry and flow rate of the coatingvapors while maintaining the fluorine doped tin oxide film 36substantially crystalline. In this non-limiting embodiment of theinvention, the crystal size of the fluorine doped tin oxide film 36 ofthe ECG and 52 of the Standard Coated Glass is reduced by adding dopantsor alloying constituents, e. g. phosphorus, boron and mixtures thereof,to the coating chemistry to change the crystal structure of the coating.Although the discussion of this non-limiting embodiment of the inventionis directed to the addition of phosphorous to the fluorine doped tinoxide film 38 of the ECG, unless indicated otherwise the discussion isapplicable to the fluorine doped tin oxide film 52 of the StandardCoated Glass, and any other type of conductive electrically conductivefilm deposited on a substrate.

As discussed above (see Table 2), the coating chemistry includes TFA,MBTC and water. In the non-limiting embodiment of the invention underdiscussion, the dopant added to change the crystalline structure of thefluorine doped tin oxide is phosphorous, and the phosphorus precursor istriethylphosphite (TEP). In this non-limiting embodiment of theinvention under discussion, the crystal size of the fluorine doped tinoxide layer is reduced by increasing the TEP/MBTC ratio. As will beappreciated, the tin oxide film 56 having the additions of phosphorouscan be deposited on or over the color suppression film 30 (FIG. 2), thelayer 42 (FIG. 3), the layer of fluorine doped tin oxide film 56,between two layers of fluorine doped tin oxide film, and/or the surface32 of the glass ribbon 20 (FIG. 4).

A discussion relating to the use of phosphorous as a breaker layer toreduce the growth of crystal size of a coating as the coating thicknessincreases is found in U.S. Pat. No. 6,797,388, which patent isincorporated herein by reference.

The following discussion is directed to the phosphorous-alloyed,fluorine doped tin oxide film 56 deposited on the color suppression film30 shown in FIG. 2, however, the discussion is applicable, unlessindicated otherwise, to depositing the phosphorous-fluorine doped tinoxide film 56 on the color suppression layer 42 (see FIG. 3) and/or onthe surface 32 of the glass ribbon 20 (see FIG. 4). In one non-limitingembodiment of the invention, the tin precursor MBTC and the fluorineprecursor TFA are vaporized and mixed with vapors of the phosphorousprecursor TEP. The vapors of the MBTC, TFA, TEP, water and carrier gasare individually moved into a coating cell, mixed and the mixed vaporsare moved out of the coating cells by the nitrogen gas as discussedabove.

The chemistry for the ECG shown in Table 2 has a TEP/MBTC ratio of zerobecause there is no addition of TEP. As can be appreciated by thoseskilled in the art, as the ratio of TEP/MBTC increases the sheetresistance and the emissivity increase because adding phosphorousreduces the carriers and thus the conductivity. In one non-limitingembodiment of the invention, the TEP/MBTC ratio is in the range 0 to0.4; preferably in the range 0 to 0.3; more preferably in the range ofgreater than 0 to 0.25, and most preferably, in the range 0.15 to 0.25.

The invention is not limited to the use of phosphorous to provide anamorphous doped tin oxide film. More particularly, the inventioncontemplates using boron and mixtures of phosphorous and boron. Boronprecursors that can be used in the practice of the invention include,but are not limited triethyl borate and trimethyl borate. In onenon-limiting embodiment of the invention, the boron precursor/MBTC ratiois in the range of greater than 0 to 0.4; preferably in the range 0 to0.3; more preferably in the range 0 to 0.25, and most preferably, in therange 0.15 to 0.25.

In the discussion of the non-limiting embodiments of the inventionpresented in Sections 1 and 2 above, the glass ribbon had a thickness of3.2 millimeters, however, the invention is not limited thereto, and theinvention can be practiced on glass ribbon or moving substrates havingany thickness, e.g. but not limited to 2.5 mm, 4.0 mm, 5.0 mm, 6.0 mmand 12.0 mm. As is appreciated by those skilled in the art of glassmaking, the ribbon or moving substrate speed decreases as the thicknessof the ribbon or moving substrate increases, and the speed increases asthe thickness of the ribbon or moving substrate decreases. Because ofthe change in ribbon or substrate speed, the flow rates of the coatingprecursors and mixed vapors is decreased as the glass ribbon thicknessdecreases and is increased as the glass ribbon thickness is increased toobtain similar or the same coating thickness as the ribbon speed orsubstrate speed changes for different glass thicknesses.

Changing the chemistry for CVD coating because of a change to glassribbon thickness is well known in the art, and no further discussion isdeemed necessary.

Section (3) Non-Limiting Embodiments of the Invention Directed to theUse of the Coated Substrates of Sections (1) and (2).

In this Section 3, the coating film 36 and 56 of the invention isdiscussed for use as a component of a window, an organic light emittingdiode device (hereinafter also referred to as “OLED”) and thin filmsolar cells, however, as is appreciated by those skilled in the art, theuse of the coating film of the invention is not limited thereto and thecoating film of the invention can be used in any article of manufacturewhere a functional coating film having electrical conductivity and/orlow emissivity is a parameter of the article of manufacture. In thefollowing discussion, reference is made to the coating film 36 of theinvention applied over or on the gradient color suppression film 30(shown in FIG. 2), however, unless indicated otherwise, the discussionis applicable to the coating film 56 of the invention, and the fluorinedoped tin oxide film 52 of the Standard Coated Glass, over or on thecolor suppression film 36, and the coating films 36 and 56 of theinvention, and coating film 52 of the Standard Coated Glass applied overor on the color suppression film 42 (shown in FIG. 3) or applied on orover a surface of the substrate (shown in FIG. 4).

With reference to FIG. 7 there is shown a coated glass 60 incorporatingfeatures of the invention. The coated glass 60 includes the gradientcolor suppression film 30 applied to surface 62 of a glass substrate 64,and the fluorine doped tin oxide film 36 of the invention over the colorsuppression film 30. A solar control coating 66 is over surface 68 ofthe glass substrate 64 opposite to the surface 62 of the substrate 64.The invention is not limited to the solar control coating 66, and thecoating 64 can be any of the types of solar control coatings known inthe art, e.g. but not limited to pyrolytic CVD coatings, spray coatingsand magnetron sputtered vacuum deposited (“MSVD”) coatings. In thepreferred embodiment of the invention, the coating 66 is an MSVD solarcontrol coating 66, e.g. a low-e coating having one or more silver films70 between dielectric films 72, e.g. but not limiting to the invention,low-e coatings of the type disclosed in U.S. Pat. Nos. 6,833,194 and5,552,180, which patents are incorporated herein by reference.

As is appreciated by those skilled in the art, the MSVD coating 66 ofthe coated glass 60 is not as durable as the pyrolytically depositedcoating 36, and the general practice is to secure the coated glass 60with the MSVD coating 66 facing the interior of an insulating unit, e.g.but not limited to the insulating unit disclosed in U.S. Pat. No.5,655,282, which patent is incorporated herein by reference. Moreparticularly and with reference to FIG. 8, there is shown an insulatingunit 76 incorporating features of the invention. The unit 76 includes aU-shaped spacer frame 78 having a moisture impervious adhesive layer 80on outer surface 82 of legs 84 and 86 of the U-shaped spacer frame 78 tosecure an uncoated glass sheet 88 to the surface 82 of the legs 84 ofthe spacer frame 78 and to secure the coated glass 60 to the outersurface 82 of the leg 86 of the spacer frame 78 with the MSVD coating 66facing interior 90 of the unit 76. Further, as is appreciated by thoseskilled in the art, it is preferred, but not limiting to the invention,to remove the coating 66 from the marginal edges 92 of the surface 68 ofthe sheet 60 to provide a better moisture impervious seal between thesurface 68 of the sheet 64 and the outer surface 82 of the leg 86 of thespacer frame 78. For a detailed discussion on the method of fabricatingmulti-sheet insulating units reference can be made to U.S. Pat. No.5,655,282.

With reference to FIG. 9, there is shown another non-limiting embodimentof a multi-sheet unit of the invention designated by the number 100. Theinsulating unit 100 of FIG. 9 is similar, but not identical to theinsulating unit in FIG. 8. More particularly, the color suppressionlayer 30 and the fluorine doped tin oxide film 36 is removed from thesurface 62 of the glass substrate 64 of the coated sheet 66, and thecolor suppression layer 30 and the fluorine doped tin oxide film 36 isapplied to outer surface 102 of the glass sheet 88.

In general, a multi sheet unit having only one surface of the foursurfaces of the two glass sheets coated with the fluorine doped tinoxide film 36 is expected to have a center of glass (COG) R value ofequal to or greater than 3; a multi sheet unit having only one surfaceof the four surfaces of the two glass sheets coated with the MSVDcoating 64 is expected to have a COG R value of equal to or greater than4, and a multi-sheet unit having one surface of the four surfaces of thetwo glass sheets coated with the fluorine doped tin oxide film 36 and asecond surface of the four surfaces coated with the MSVD coating 64,e.g. as shown in FIGS. 8 and 9 is expected to have a COG R value ofequal to or greater than 5.

The “R” value is a commercial unit used to measure the effectiveness ofthermal insulation. The R value of a thermal insulator, e.g. amulti-sheet unit is defined to be 1 divided by the thermal conductanceper inch as measured between outer surfaces of the insulating unit.

The discussion is now directed to using the doped tin oxide film of theinvention as an anode for an OLED device. In the following discussion,reference is made to the coating film 36 of the invention applied overor on the gradient color suppression film 30 (shown in FIG. 2), however,unless indicated otherwise, the discussion is applicable to the coatingfilm 56 of the invention, and the fluorine doped tin oxide film 52 ofthe Standard Coated Glass, over or on the color suppression film 36, andthe coating films 36 and 56 of the invention, and coating film 52 of theStandard Coated Glass applied over or on the color suppression film 42(shown in FIG. 3) or applied on or over a surface of the substrate(shown in FIG. 4).

An exemplary OLED device that can be used in the practice of theinvention is described in U.S. Pat. No. 7,663,300, which patent ishereby incorporated by reference. An exemplary OLED designed by thenumber 110 is shown in FIG. 10. The OLED 110 includes a cathode(negative polarity) 112, which can be any conventional OLED cathode.Examples of suitable cathodes include metals, such as but not limitedto, barium and calcium. The cathode typically has a low work function.An emissive layer 114 over or on the cathode can be a conventionalorganic electroluminescent layer as known in the art. Examples of suchmaterials include, but are not limited to, small molecules such asorganometallic chelates (e.g., Alq3), fluorescent and phosphorescentdyes, and conjugated dendnmers. Examples of suitable materials includetriphenylamine, perylene, rubrene, and quinacridone. Alternatively,electroluminescent polymeric materials are also known. Examples of suchconductive polymers include poly(p-phenylene vinylene) and polyfluorene.Phosphorescent materials could also be used. Examples of such materialsinclude polymers such as poly(n-vinylcarbazole) in which anorganometallic complex, such as an iridium complex, is added as adopant. An anode 118 of the OLED 110 can be a conductive, transparentmaterial, such as a metal oxide material, such as, but not limited to,the doped tin oxide of the invention. The anode typically has a highwork function.

With continued reference to FIG. 10, in the preferred practice of theinvention, the anode (positive polarity) 118 includes the fluorine dopedtin oxide layer 36 and the color suppression layer 30 on the glasssubstrate 22. The structure and operation of a conventional OLED deviceare well known in the art and will be understood by one of ordinaryskill in the art without further discussion.

The discussion is now directed to using the doped tin oxide film of theinvention as an electrode for a solar cell. In the following discussion,reference is made to the coating film 36 of the invention applied overor on the gradient color suppression film 30 (shown in FIG. 2), however,unless indicated otherwise, the discussion is applicable to the coatingfilm 56 of the invention, and the fluorine doped tin oxide film 52 ofthe Standard Coated Glass, over or on the color suppression film 36, andthe coating films 36 and 56 of the invention, and coating film 52 of theStandard Coated Glass applied over or on the color suppression film 42(shown in FIG. 3) or applied on or over a surface of the substrate(shown in FIG. 4).

Shown in FIG. 11 is a solar cell 120 have a photovoltaic cell 124 andelectrodes 126 and 128. The electrode 128 includes the fluorine dopedtin oxide film 36, the color suppression layer 30 and the glasssubstrate 22.

As can now be appreciated, the invention is not limited to thenon-limiting embodiments of the invention presented herein and thefeatures of the non-various limiting embodiments of the invention can beused with one another. It will further be readily appreciated by thoseskilled in the art that modifications can be made to the non-limitingembodiments of the invention without departing from the conceptsdisclosed in the foregoing description. Accordingly, the particularnon-limiting embodiments of the invention described in detail herein areillustrative only and are not limiting to the scope of the invention,which is to be given the full breadth of the appended claims and any andall equivalents thereof.

What is claimed is:
 1. A coated glass sheet, comprising: a glasssubstrate having a surface, and an electrically conductive film over thesurface of the glass substrate, comprised of a pyrolytic chemical vapordeposited doped tin oxide film over the surface of the glass substrate,wherein dopant of the doped tin oxide film is fluorine and a co-dopantor alloying constituent selected from the group of phosphorous, boronand mixtures of phosphorous and boron.
 2. The coated glass sheetaccording to claim 1, wherein a first electrically conductivefluorine-doped tin oxide film is between the surface of the substrateand the electrically conductive film and a second electricallyconductive fluorine-doped tin oxide film is over the electricallyconductive film to position the electrically conductive film between thefirst and the second electrically conductive fluorine-doped tin oxidefilms.
 3. The article of manufacturing coated glass according to claim 1wherein surface of the conductive film has a coefficient of friction ofless than 1.2.
 4. The electrolytically conductive film of claim 1,comprised of a pyrolytic chemical vapor deposited doped tin oxide filmover the surface of the glass substrate, wherein the pyrolytic chemicalvapor deposited fluorine doped tin oxide film comprises a sheetresistance in the range of 9.5 to 14.0 ohms/square; an emissivity rangeof 0.14 to 0.17 and an absorption coefficient of greater than 1.5×10³cm⁻¹ in the wavelength of 400-1100 nanometers, and a surface height meansquare of less than 15 nanometers, wherein the properties are determinedat a substrate thickness of 3.2 millimeters.
 5. An article ofmanufacture, comprising: a glass substrate, and an electricallyconductive film over a surface of the glass substrate, the conductivefilm selected from a group comprising Embodiment B wherein theconductive film of Embodiment B comprises a phosphorous-fluorine dopedtin oxide pyrolytically deposited film over the surface of the glasssheet, wherein coating vapor of the deposited film comprises a tinprecursor, a phosphorous precursor and a fluorine precursor.
 6. Thearticle of manufacture according to claim 5 wherein the surface of thesubstrate is a first surface and further comprising the substrate havinga second surface opposite to the first surface and a coating over thesecond surface.
 7. The article of manufacture according to claim 6wherein the coating over the second surface of the substrate is amagnetron sputtered vacuum deposited coating comprising a metal filmbetween a pair of dielectric films.
 8. The article of manufactureaccording to claim 7 wherein the substrate is a coated first sheet of aninsulating unit, wherein the insulating unit comprises a spacer framehaving a first layer of an adhesive on first outer surface of the spacerframe and a second layer of the adhesive on opposite second outersurface of the spacer frame, wherein the first layer of adhesive securesthe coated first sheet to the first outer surface of the spacer framewith the sputtered coating facing an interior of the spacer frame, andthe second layer of the adhesive securing a second sheet to the secondouter surface of the spacer frame.
 9. The article of manufactureaccording to claim 5 wherein the substrate is a coated first sheet of aninsulating unit, wherein the insulating unit comprises a spacer framehaving a first layer of an adhesive on first outer surface of the spacerframe and a second layer of the adhesive on opposite second outersurface of the spacer frame, wherein the first layer of adhesive securesthe coated first sheet to the first outer surface of the spacer framewith the conductive mm facing an exterior of the spacer frame, and thesecond layer of the adhesive securing a second sheet to the second outersurface of the spacer frame.
 10. The article of manufacture according toclaim 9, wherein the second sheet has a first surface and an oppositesecond surface with the first surface of the second sheet facing aninterior of the spacer frame, and further comprising a coating over thefirst surface of the second sheet.
 11. The article of manufactureaccording to claim 10 wherein the coating over the second surface of thesubstrate is a magnetron sputtered vacuum deposited coating comprising ametal film between a pair of dielectric films.
 12. The article ofmanufacture according to claim 5 wherein the substrate having theconductive film is an anode of an organic light emitting diode devicehereinafter referred to as an “OLED”, the OLED comprising an emissivelayer and one or more light emitting layers between the anode and acathode.
 13. The article of manufacture according to claim 5 wherein thesubstrate having the electrically conductive film is an electrode for asolar cell device, the solar cell comprising a photovoltaic layerbetween the first electrode and a second electrode.
 14. The article ofmanufacture of claim 5, wherein the ratio of the phosphorous precursorto the tin precursor is in the range of greater than 0 to 0.4.